WO1990007477A1 - Composition refractaire prete au durcissement et sa preparation - Google Patents

Composition refractaire prete au durcissement et sa preparation Download PDF

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Publication number
WO1990007477A1
WO1990007477A1 PCT/FR1989/000682 FR8900682W WO9007477A1 WO 1990007477 A1 WO1990007477 A1 WO 1990007477A1 FR 8900682 W FR8900682 W FR 8900682W WO 9007477 A1 WO9007477 A1 WO 9007477A1
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Prior art keywords
binder
saponification
primary
filler
refractory
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PCT/FR1989/000682
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English (en)
French (fr)
Inventor
Gérard RICHARD
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Societe D'applications De Procedes Industriels Et Chimiques S.A.P.I.C.
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Application filed by Societe D'applications De Procedes Industriels Et Chimiques S.A.P.I.C. filed Critical Societe D'applications De Procedes Industriels Et Chimiques S.A.P.I.C.
Priority to KR1019900701917A priority Critical patent/KR970009991B1/ko
Priority to AU48269/90A priority patent/AU647379B2/en
Priority to DE68927181T priority patent/DE68927181T2/de
Priority to EP90900885A priority patent/EP0451181B1/fr
Publication of WO1990007477A1 publication Critical patent/WO1990007477A1/fr

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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632—Organic additives
    • C04B35/634—Polymers
    • C04B35/63448—Polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B35/63472—Condensation polymers of aldehydes or ketones
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/66—Monolithic refractories or refractory mortars, including those whether or not containing clay
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
    • B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
    • B22C1/20—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
    • B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
    • B22C1/20—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents
    • B22C1/22—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
    • B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
    • B22C1/20—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents
    • B22C1/24—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of oily or fatty substances; of distillation residues therefrom
    • C—CHEMISTRY; METALLURGY
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632—Organic additives
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632—Organic additives
    • C04B35/634—Polymers
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632—Organic additives
    • C04B35/634—Polymers
    • C04B35/63492—Natural resins, e.g. rosin
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    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/0087—Uses not provided for elsewhere in C04B2111/00 for metallurgical applications
    • C04B2111/00887—Ferrous metallurgy
    • C—CHEMISTRY; METALLURGY
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3418—Silicon oxide, silicic acids or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
    • C04B2235/422—Carbon
    • C—CHEMISTRY; METALLURGY
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • C04B2235/9669—Resistance against chemicals, e.g. against molten glass or molten salts
    • C04B2235/9676—Resistance against chemicals, e.g. against molten glass or molten salts against molten metals such as steel or aluminium

Definitions

  • the present invention relates to a refractory composition, ready for cold or hot curing, of the type comprising: a) a charge of refractory mineral grains with high mechanical characteristics, for example silica, alumina, carbon, b) at least one primary or principal binder of the thermosetting type, for agglomerating the grains of said filler suitable for said filler, and c) at least one secondary binder intended to improve and / or correct the defects of the primary binder, said Etan composition especially intended for the manufacture of molds and cores for foundries, for the manufacture of bricks and rammed earth and for the manufacture of plugging masses for tapholes of blast furnaces.
  • a refractory composition ready for cold or hot curing, of the type comprising: a) a charge of refractory mineral grains with high mechanical characteristics, for example silica, alumina, carbon, b) at least one primary or principal binder of the thermosetting type, for agglomerating the grains of said filler suitable for said filler,
  • the refractory compositions targeted by the present invention relate to all the fields in which a refractory product must be molded and have temporary or permanent mechanical characteristics.
  • the first of the two most common current techniques consists in using a mixture of a refractory charge in grains (for example of silica, chamotte, chromite zircon) associated in small proportion, generally between 0, 7 and 2% of the weight of the filler, for the agglomeration between them of the grains of said filler, with at least one primary or main binder chosen from thermosetting resins which can be polymerized either hot or cold, and in the latter case using a hardener or a catalyst, liquid or gaseous, introduced into the composition the instant of its hardening.
  • a refractory charge in grains for example of silica, chamotte, chromite zircon
  • at least one primary or main binder chosen from thermosetting resins which can be polymerized either hot or cold, and in the latter case using a hardener or a catalyst
  • the second of the two most widespread techniques similar to the first aforementioned technique as regards its implementation, consists in using an alkali silicate or a natural or synthetic clay as primary or main lian.
  • silanes which improve the adhesion of the binder on the grains of the filler.
  • the advantage of silanes is that they make it possible to obtain molds and foundry cores having good mechanical characteristics, and that they allow subsidiary-
  • coal tar which constitutes a binder generally giving satisfaction in terms of agglomeration of the grains of the filler.
  • the coal tar gives off considerable amounts of smoke when such refractory compositions are brought to high temperature.
  • these fumes are unpleasant for the personnel but also and above all they are toxic and carcinogenic, and consequently the prohibition to use coal tar for the aforementioned purposes has already been ordered in certain countries.
  • these organic binders have their own drawbacks: they do not allow the grains of the refractory mass to be agglomerated correctly; their use requires very high employment percentages, of the order of 12 to 15% by weight of the granular filler to be agglomerated; they require the simultaneous addition to the charge of their solvents, with which obviously volatile materials are introduced, generally harmful, which are released on contact with heat.
  • the refractory compositions intended for the manufacture of sealing masses therefore remain uneconomical and, in addition, whatever the binder used, they always give off fumes, charged and often toxic, during their use: the use of such refractory compositions is therefore limited.
  • silanes to replace part of the synthetic binders, such as phenol-for maldehyde resin or furan resin, has not proved to be of any effectiveness in the field of the manufacture of capping compositions, and in practice the percentages of synthetic binders remain at least 12 to 15% by weight relative to the granular filler to be agglomerated.
  • the binders never give their characteristics in an optimal manner. If they are used in very small percentages, the binders obviously never succeed in completely and uniformly coating the granular fillers which it is desired to agglomerate.
  • silica sand conventionally used in foundries has a specific surface of the order of 13 m 2 / kg, and that this surface must be coated with only 7 to 20 g of resin; in other words, the covering power of the binder must be 650 to 1850 m / kg, which is incommensurate compared to the covering power of a paint.
  • the present invention proposes to overcome, by a means common to the original characteristics, the drawbacks exposed above with regard to the techniques of agglomeration of the refractory compositions used: in foundries, for the manufacture of plugging masses for tap holes of tall furnaces, for the manufacture of bricks and rammed earth, and generally in any industry using a refractory material whose agglomeration involves the use of at least one thermosetting binder with temporary or permanent effect.
  • wetting additive instead of being a simple surface-active agent, is replaced by a new product having at the same time its own binding properties and specific wetting and film-forming properties, the result must be significantly improved.
  • this improvement must be all the more important since, by using an agent other than a simple surfactant, one is no longer limited by the percentage very low incorporation specific to simple surfactants.
  • modified secondary binder which, if correctly chosen, combines: a) a binder and film-forming effect, with properties complementary to those of the primary binder thermosetting, and consequently adapted the desired application as is already said primary binder, b) emulsifying qualities such that they allow excellent compatibility with the thermosetting primary binder, c) specific wetting properties such as the secondary binder and the thermosetting primary binder, then closely associated, perfectly coating the charge of grains to be agglomerated.
  • the wetting and emulsifying properties of the secondary binder allow a very significant reduction in the quantities of products used, the corollary of this reduction is that it is then possible to produce, ready for hardening, refractory compositions with very low volatile matter content: the risks of pollution are then almost nonexistent provided that all the basic components are chosen correctly, in particular the primary binder (s) and the secondary binder (s).
  • the present invention therefore has for first object a refractory composition, ready for hardening cold or hot, of the type comprising: a) a charge of refractory mineral grains with high mechanical characteristics, for example of silica, alumina, carbon, b) at least one primary or main binder, of thermosetting type for agglomerating the grains of said filler between them, suitable accordingly for said filler, and c) at least one secondary binder intended to improve and / or correct defects primary binder, said composition being in particular intended for the manufacture of molds and cores for foundry, for the manufacture of bricks and rammed earth and for the manufacture of plugging masses for tapholes of blast furnaces, and being characterized in that that the secondary binder is obtained by saponification of a carbon product having an acid number sufficient to be modifiable by saponifica- tion, said secondary binder, by its own emulsifying properties, thus being made compatible with the primary binder.
  • a refractory composition ready for hardening cold or hot
  • the saponification is preceded by an esterification if it is not sufficiently achievable directly.
  • the present invention has for second object a secondary binder intended, in mixture with at least one primary or main binder, of thermosetting type, to agglomerate between them the grains of a load of refractory mineral grains with high mechanical characteristics, for example silica, alumina, carbon, characterized in that it is obtained by saponification of a carbon product having an acid number sufficient to be modifiable by saponification.
  • a third object of the present invention is a composite binder formed from at least one primary thermosetting binder suitable for the filler to be agglomerated and from at least one secondary binder corresponding to the above-mentioned characteristic.
  • the secondary binder thus brings to the main binder its own binding and film-forming properties.
  • the secondary binder thus defined brings, thanks to its own emulsifying properties, great compatibility with many primary binders, which would not exist without saponification, thus allowing the production of homogeneous composite binders.
  • the present invention therefore has another object as a method of manufacturing a composite binder, characterized in that the carbon product which can be modified by saponification, constituting after saponification the secondary binder, is used as a total or partial substitution for the Conden ⁇ tion normally used in the development of an alkaline condensation resin intended to constitute the primary binder, and thus leading to the creation of a new type of hybrid but homogeneous binder, with new characteristics and improved wetting properties.
  • the present invention has as its fourth object a process for the preparation, with a view to its hardening, of a refractory composition of the type comprising: a) a filler of refractory mineral grains with high mechanical characteristics, for example of silica, of alumina , of carbon, b) at least one primary or main binder, of thermosetting type, suitable for the agglomeration of the grains of the filler in question, and c) at least one secondary binder intended to improve and / or correct the defects of the primary binder, said composition being in particular intended for the manufacture of molds and cores for foundry, for the manufacture of bricks and rammed earth and for the manufacture of plugging masses for tapholes of blast furnaces, said process being characterized in that that is added either to the mass of the filler and of the primary binder, before the filler has hardened, or to the primary binder before it is mixed with the filler, either charged before or during the incorporation of the primary binder, a secondary binder obtained by sapon
  • the carbonaceous product which after saponification constitutes the secondary binder, is chosen from the wide range of natural and synthetic products capable of both: - in its natural state, showing film-forming properties and agglomerating qualities, cold or hot depending on the uses, and
  • thermosetting base binder In the modified state by saponification, to have surface-active properties intended to improve the wetting of the refractory charges to be agglomerated, and emulsifying properties such that it is as completely as possible compatible with the thermosetting base binder.
  • the acid number of the carbon product modifiable by saponification is between 40 and 300. This value of acid number is that of the basic carbon product, that is to say before the possible esterification at which will be subject to said product if the saponification is not sufficiently achievable directly.
  • the secondary binder preferably constitutes between 10 and 60% of the composite binder (primary (s) + secondary (s)).
  • thermosetting binders used primarily, these binders, natural or synthetic, being mineral (raw or activated clays, for example alkali silicates) or organic (for example fatty acids, acrylics, - alkyds, aminoplasts, coumarone, hydrocarbon derivatives, epoxy, furans, vegetable oils, indene, phenoplasts, polyesters, polyurethanes, natural resins).
  • mineral raw or activated clays, for example alkali silicates
  • organic for example fatty acids, acrylics, - alkyds, aminoplasts, coumarone, hydrocarbon derivatives, epoxy, furans, vegetable oils, indene, phenoplasts, polyesters, polyurethanes, natural resins.
  • the secondary binder associated with the primary binder in accordance with the invention may be incorporated in addition to or in replacement of part of said primary binder.
  • the secondary binder will be used to replace part of the primary binder, and all the more so that when implementing the invention it is easy to provide a quantity of composite binder (primary + secondary) less than the quantity of the same primary binder that it is necessary to incorporate by applying traditional techniques (in particular for the manufacture of plugging masses and for the manufacture of bricks and adobe).
  • thermoplastic binders such as polyvinyl alcohol (PVA) and a copolymer of vinyl acetate and ethylene (EVA).
  • PVA polyvinyl alcohol
  • EVA vinyl acetate and ethylene
  • thermoplastic binder in order to obtain a more easily moldable ceramic paste, it is also known to saponify part (generally between 20% and 90%) of these thermoplastic binders.
  • saponify part generally between 20% and 90%
  • the thermoplastic binder thus saponified is only temporary; indeed, the binder must be able to soften at a temperature below 130 ° C, and in any event at a temperature which is never higher than 160 ° C, and furthermore said binder is called to decompose quickly, at relatively low temperature, of the order of 200 ° C, and without leaving carbon residues;
  • the saponified thermoplastic binder used in the molding of ceramics is very soluble in water and that it is used in a necessarily aqueous medium, in the presence of a non-negligible amount of water, so as to then be able to develop the properties of said ceramic materials, whereas, conversely, the thermosetting binder according to the present invention is used in an anhydrous medium, or in the presence of only a few traces of water since the latter is a poison which, when reacting with molten metal, always causes surface defects and also in some cases causes explosions
  • the composite binder can be mixed with the filler in an amount of the order of:
  • Example 1
  • the secondary binder ' is in this case advantageously chosen from natural resins, synthetic thermoplastic resins, or also from talloils whose contents of resin acids can be chosen according to the goal to be achieved.
  • the secondary binder replaces part 5 of the primary binder
  • the desired flexibility result can be achieved, but the mechanical characteristics of the sand in the molds or cores are then so weak, due to the physical incompatibilities between the two binders which somehow form a heterogeneous mixture, which the molding and casting operations cannot take place correctly, nor without risk for the quality of the parts to be produced.
  • the invention here assumes all its importance since, from the moment when the secondary binder is correctly modified, it becomes fully compatible with the resin constituting the primary binder. Therefore, the agglomerating qualities of the composite binder thus formed, which combines mechanical characteristics and flexibility when hot, make it possible to avoid the 5 cracks of the steel parts.
  • the "modified" secondary binder is therefore a resin or tall oil emulsified with a mineral base (for example baryte, lime, lithine, soda, potash, or their salts, alkali alcoholates ) or with an organic base, (for example amino, ammonia).
  • a mineral base for example baryte, lime, lithine, soda, potash, or their salts, alkali alcoholates
  • an organic base for example amino, ammonia
  • the modification by saponification of the binder secondary hydrocarbon of origin with an appropriate base then allows its emulsification with the traditional primary binder and gives the composite binder thus produced wetting properties of the siliceous filler such as the quantities of hydrocarbon binder necessary to obtain beautiful parts, without having to pass from 5 layer of coating on the molds and cores, are greatly reduced.
  • the harmful gas evolution is of course also reduced by the same amount.
  • an excellent composite binder for casting castings without interposing a layer of refractory coating is obtained by mixing at 60/70 ° C: - 1O _ 60 parts of furan resin 70% furfuryl alcohol , or resol type phenolic resin,
  • another composite binder is obtained by mixing at 50 ° C:
  • a composite binder which has the advantages of furan resins, but which also has better wetting of the mineral fillers (sand, zircon, chamotte, for example) and gives the castings a very improved appearance thanks to the presence of the linseed oil which, during casting, turns into carbon, making a protective screen at the interface
  • This composite binder gives qualities of cast parts substantially identical to those obtained in Example No. Example 6:
  • a particularly interesting composite binder from the point of view of the quality of the castings is obtained by mixing: 5 - 65 parts of phenol-urea-furan resin containing 65% furfuryl alcohol,
  • This composite binder indeed provides, at the time of the 1O casting, a progressive carbonaceous release which forms a gaseous screen at low pressure at the mold / metal interface, which ensures a good surface appearance of the parts, even without passing a layer .
  • this composite binder has the following particularities: 1- 5 - to be formed of a primary binder and two secondary binders, one of which, moreover, has been modified by esterification before being modified by saponification,
  • a composite binder comprising: 5 - ⁇ parts of high-ortho phenolic resin,
  • silicate binders very hydroscopic products
  • the use of silicate is advantageous insofar as it makes it possible to harden the granular mass after agglomeration of its grains by a stream of carbon dioxide CO 2 .
  • the addition to the primary binder of a modified and appropriate secondary binder makes it possible to limit the amount of silicate, while retaining all the advantages of this primary binder, and in particular that of harden with a current of CO 2 , and in addition by providing the additional mechanical characteristics necessary as well as protection against moisture uptake and better destruction after casting.
  • a mixture in accordance with the invention and usable in such a CO 2 hardening process is obtained by mixing: - 70 parts of sodium silicate,
  • This mixture gives a binder which reacts well and quickly to CO 2 , which has a good surface appearance on the molds and cores, and which ensures perfect resistance to storage before casting, even in a humid atmosphere, which is not the case. usually case.
  • This composite binder makes it possible to obtain very beautiful cores or molds, having a perfect surface gloss, appreciably improving the appearance of the cast parts, and this without having to resort to the passage of any "layer".
  • This gloss is due to the fact that the high reactivity furan resin (or epoxy resin, or acrylic resin) and tall oil both have a high wetting power.
  • Such a composite binder has a lubricating appearance which facilitates the release of the molds and cores produced by this process; in addition, it considerably reduces the fouling of tools (models and core boxes), which has the advantage of improving productivity.
  • Example 10
  • a modified secondary binder is added to the primary binder (natural clay, or bentonite with or without starch added), it is possible to better still coat the sand, with less water, and thus obtain parts of perfect quality, which do not allow conventional compromises (if the sand is regenerated instead of being new, and therefore already contains a modified secondary binder residue, the addition of 0.05 to 0.2% of this secondary binder will generally be sufficient).
  • a mixture comprising:. - 70 parts of tall oil (or other vegetable oil),
  • liquid additive which, as a secondary binder, advantageously replaces solid carbon additives and which has several advantages: a) total absence of toxicity during the casting of the parts, unlike the toxicity of cast according to old techniques due to the fact that petroleum pitch and pulverized coal give off at the time of pouring benzopyrene, which is a highly carcinogenic product, b) liquid presentation, therefore easy to dose, and clean unlike blacks and pitches in powder, c) better wetting of the sand, allowing lower utilization rates with equal result, d) beautiful surface appearance of the parts, with better regularity, the carbonaceous gas evolution taking place much more gradually, therefore with less pressure, and thus avoiding the defects due to the gases which often appear in "green” molding when the addition of carbonaceous product is a little too strong.
  • the secondary binder corresponding to the formulation expressed above also gives very interesting technical results in steel foundry.
  • the wetting properties of this additive improves the "tightening", therefore the surface appearance of the molds (which will be found on the surface of the casting), and on the other hand the gas evolution is so progressive during casting that it does not react not with the liquid metal, but only constitutes a "screen” which protects the sand from the metal, thus giving parts of a quality and a very markedly improved appearance.
  • Example 11 Example 11:
  • an excellent composite binder for plugging mass for blast furnaces is obtained by emulsifying:
  • the composite binder comprising a furan resin and tall oil soap, obtained by saponification of tall oil with potash, gives the desired mechanical characteristics with half the binder and without any other addition of solvent, plasticizer or wetting agent.
  • the refractory mass thus produced with 6 to 10% of the composite binder in accordance with the invention has all the qualities required, namely: a) ease of extrusion, b) good heat resistance up to 120 / 130 ° C, c) rapid setting above 200 ° C ensuring better productivity of the blast furnace, d) high bond strength at high temperature, e) absence of harmful gas pockets, f) healthy environment thanks to the elimination of harmful and toxic volatile emissions, g) good resistance to erosion by liquid iron and slag, h) conservation of the mass during prolonged storage of several month.
  • Another plugging mass for blast furnace tap holes which meets the new hygienic standards imposed, can be obtained by using a phenolic resin added with tall oil soap and, optionally, tall oil pitch soap .
  • resinous primary binders and mainly phenolic resin, are used at a rate of 10 to 15% (possibly in combination with other secondary binders which have not undergone any modification in accordance with the invention), thereby introducing significant quantities of free phenol which, both cold and hot, have a certain toxicity, although less than that of tars.
  • This composite binder added to the usual refractories used to make the sealing masses (clay, alumina, silica, silicon carbide, chamotte, graphite, for example), is used to replace the usual tar with an improved hardening time, excellent mechanical and chemical resistance to slag.
  • This binder is also completely non-toxic, unlike tar and phenolic resins used in high percentage.
  • Such a composite binder exhibits wetting qualities.
  • the modified secondary binder provides wetting qualities of alkaline refractory charges (magnesia or other) such that the amount of overall binder required becomes more reasonable and economical.
  • alkaline refractory charges magnesia or other
  • the resin of the primary binder is of the alkaline condensation type (phenolic, urea formaldehyde, furan, for example), that is to say for simplification almost all of the resins with the exception of the novolaks
  • the secondary binder as a condensing agent during the manufacture of the primary binder: the composite binder consisting of "alkaline condensing resin, saponifiable carbon product and base" is then produced in a single operation .
  • the introduction of the secondary binder into the mass to be hardened it is quite clear that it can be done:

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Ceramic Products (AREA)
  • Mold Materials And Core Materials (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Compositions Of Oxide Ceramics (AREA)
PCT/FR1989/000682 1988-12-28 1989-12-27 Composition refractaire prete au durcissement et sa preparation WO1990007477A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
KR1019900701917A KR970009991B1 (ko) 1988-12-28 1989-12-27 경화 가능한 내화성 조성물, 이조성물에 도입되는 부결합제와 복합결합제, 및 상기의 경화 가능한 내화성 조성물의 제조방법
AU48269/90A AU647379B2 (en) 1988-12-28 1989-12-27 Refractory composition ready for hardening and its preparation
DE68927181T DE68927181T2 (de) 1988-12-28 1989-12-27 Feuerfeste zubereitung, fertig zum härten und zubereitung
EP90900885A EP0451181B1 (fr) 1988-12-28 1989-12-27 Composition refractaire prete au durcissement et sa preparation

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FR88/17348 1988-12-28
FR8817348A FR2640965B1 (enrdf_load_stackoverflow) 1988-12-28 1988-12-28

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JP (1) JP2865420B2 (enrdf_load_stackoverflow)
KR (1) KR970009991B1 (enrdf_load_stackoverflow)
AT (1) ATE142610T1 (enrdf_load_stackoverflow)
AU (1) AU647379B2 (enrdf_load_stackoverflow)
CA (1) CA2006648A1 (enrdf_load_stackoverflow)
DE (1) DE68927181T2 (enrdf_load_stackoverflow)
ES (1) ES2094147T3 (enrdf_load_stackoverflow)
FR (1) FR2640965B1 (enrdf_load_stackoverflow)
WO (1) WO1990007477A1 (enrdf_load_stackoverflow)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0220491A2 (en) * 1985-09-24 1987-05-06 Kuraray Co., Ltd. Water-soluble binder and hot-melt binder for molding ceramics
EP0269788A1 (de) * 1986-11-05 1988-06-08 Rütgerswerke Aktiengesellschaft Ungeformte, feuerfeste Massen
US4765950A (en) * 1987-10-07 1988-08-23 Risi Industries, Inc. Process for fabricating parts from particulate material

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Publication number Priority date Publication date Assignee Title
JPS5946488B2 (ja) * 1978-08-07 1984-11-13 極東脂肪酸株式会社 アレルギ−反応抑制剤
JPS6054967A (ja) * 1983-09-02 1985-03-29 日本合成化学工業株式会社 セラミツクバインダ−

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0220491A2 (en) * 1985-09-24 1987-05-06 Kuraray Co., Ltd. Water-soluble binder and hot-melt binder for molding ceramics
EP0269788A1 (de) * 1986-11-05 1988-06-08 Rütgerswerke Aktiengesellschaft Ungeformte, feuerfeste Massen
US4765950A (en) * 1987-10-07 1988-08-23 Risi Industries, Inc. Process for fabricating parts from particulate material

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
WPI Data Base, Acc No: 85-113467/19, & JP, A, 60054967 (Nippon Synth Chem Ind) 29 Mars 1985 *

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DE68927181D1 (de) 1996-10-17
AU647379B2 (en) 1994-03-24
FR2640965B1 (enrdf_load_stackoverflow) 1992-12-31
JP2865420B2 (ja) 1999-03-08
KR970009991B1 (ko) 1997-06-20
ES2094147T3 (es) 1997-01-16
AU4826990A (en) 1990-08-01
CA2006648A1 (fr) 1990-06-28
DE68927181T2 (de) 1997-04-24
EP0451181A1 (fr) 1991-10-16
FR2640965A1 (enrdf_load_stackoverflow) 1990-06-29
EP0451181B1 (fr) 1996-09-11
KR910700211A (ko) 1991-03-14
JPH04502450A (ja) 1992-05-07
ATE142610T1 (de) 1996-09-15

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